The present invention relates to a process for preparation of conductive polymer dispersion. More particularly, said process relates to preparation of poly aniline dispersion in water, in organic solvents and in mixture of solvents.
Barry et al., U.S. Pat. No. 5,240,644, prepared dispersion of polyaniline and its derivatives in the acidic aqueous reaction medium during polymerization using aromatic polyalkyleneoxides stabilizers. Aniline or its derivatives was oxidized by ferric chloride, persulfates or periodates oxidants in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using polyalkyleneoxides stabilizers (monomer to stabilizer ratio is 1:5 w/w). Removal of low molecular weight compounds, residual aniline-hydrochloride salt, initiator and stabilizer from the reaction mixture are difficult. Excess amount of stabilizer (monomer to stabilizer ratio is 1:5 w/w) is used to get stable dispersion with particle size of 600 nm.
Yang et al., U.S. Pat. No. 6,429,259, disclosed the synthesis of water soluble polyaniline containing biopolymer complex, polyaniline-bovine serum albumin, polyaniline-human serum albumin in the reaction medium with no visual particles or precipitates. Aniline was oxidized by sodium persulfate oxidant in 1:1 molar ratio (monomer to oxidant) in presence of hydrochloric acid using bovine serum albumin, human serum albumin stabilizers (monomer to stabilizer ratio is 1:10 w/w). Polyaniline dispersion was isolated by dialysis and the dispersion was stable over 6 months. In this process, large amount of stabilizer (monomer to stabilizer ratio is 1:10 w/w) is utilized in the reaction medium.
Bay et al., (Polymer, 32, 2456, 1991) reported a process for preparation of polyaniline colloids using a copolymer poly(1-vinylimidazole-co-aminostyrene) stabilizer in the reaction medium (acidic aqueous medium) during polymerization. Aniline was oxidized by potassium iodate oxidant in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using poly(1-vinylimidazole-co-aminostyrene) stabilizer (monomer to stabilizer ratio is 1:1 w/w). The obtained polyaniline particles showed a non-spherical ‘rice-grain’ morphology with particle size of 160 nm. The disadvantage of this process is the use of initiator potassium iodate, which was reduced to iodine ions and/or free iodine during the aniline polymerization. These by-products are usually incorporated in to the polyaniline colloids at relatively high levels (10-20 wt %).
Chattopadhyay et al., (Langmuir 14, 1544, 1998) utilized ethyl(hydroxyethyl) cellulose as stabilizer for dispersion polymerization of aniline in water as well as in aqueous alcohol medium. Aniline was oxidized by ammonium persulfate oxidant in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using ethyl(hydroxyethyl) cellulose as stabilizer (monomer to stabilizer ratio is 1:2 w/w). Polyaniline dispersion was isolated by dialysis and the dispersion was stable for 2 months. The particle size of polyaniline dispersion was found to be 100-300 nm with tree like morphology.
Banerjee et al., (Langmuir 11, 2414, 1995) utilized poly(vinyl methyl ether) as stabilizer for polyaniline dispersion in aqueous or aqueous organic medium during polymerization. Aniline was oxidized by ammonium persulfate or potassium dichromate oxidant in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using poly(vinyl methyl ether) as stabilizer (monomer to stabilizer ratio is 1:2.5 w/w). Poly (vinyl methyl ether) is unique stabilizer in the sense that it allows redispersion of the isolated polyaniline particles in both aqueous and organic media by virtue of being soluble in water and in number of organic solvents. The polyaniline dispersion was isolated by centrifuging the mixture and the dispersion was stable for two months. The particle size of polyaniline dispersion was 195 nm with oblong morphology.
S. P. Armes et al., (Langmuir 6, 1745, 1990) synthesized colloidal polyaniline dispersion in acidic aqueous solution using poly (2-vinylpyridine-co-p-aminostyrene) stabilizer. Aniline was oxidized by potassium periodate oxidant in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using poly (2-vinylpyridine-co-p-aminostyrene) as stabilizer (monomer to stabilizer ratio is 1:1 w/w). The polyaniline was isolated by centrifuging the mixture and the dispersion in acidic aqueous medium was stable for one and a half months. The particle size of polyaniline dispersion was 150 nm with rice grain morphology.
Stejskal et al., (Polymer 40, 2487, 1999) synthesized polyaniline dispersion using hydroxypropylcellulose as stabilizer in acidic aqueous medium. Aniline was oxidized by ammonium persulfate oxidant in 1:1 molar ratio (oxidant to monomer) in presence of hydrochloric acid using hydroxypropylcellulose as stabilizer (monomer to stabilizer ratio is 1:2.5 w/w). Removal of low molecular weight compounds, residual aniline-hydrochloride salt, initiator and stabilizer from the reaction mixture are difficult. The free stabilizer remains in the dispersion even after dialysis and the dispersion was stable for one month. The particle size of polyaniline dispersion was 360 nm with spherical or coral like morphology.
The drawbacks of the above mentioned processes are (i) polyaniline dispersion is prepared in reaction medium during polymerization using stabilizer and the removal of low molecular weight compounds, residual aniline salt, initiator and stabilizer from the reaction mixture are difficult. (ii) polyaniline dispersion is isolated by dialysis or centrifuging the reaction mixture (ii) In some of the cases, higher amount of stabilizer is used in the preparation of polyaniline dispersion. (iii) Polyaniline dispersion is prepared mostly in aqueous-acid medium (dilute aqueous acid medium) or aqueous-organic medium.
Generally polyaniline salt decomposes without melting. As would be evident from the structures of these materials, the molecules are rather rigid and associated with high cohesive force. As a result, it is difficult, if not impossible, to process polyaniline by conventional polymer processing techniques, including molding and extrusion, which require softening or melting of the polymer or solubilizing the polymer. To overcome these problems and to improve tractability the inventors have prepared polyaniline dispersion in water and various organic solvents and/or mixture. A comparison table 2 is provided herewith to show the difference of the present processes available in prior art.